Conservative mixing of highly alkaline groundwater with hypersaline seawater at Shark Bay recorded by Ba isotopic compositions in stromatolitic carbonates

Hamelin Pool in Shark Bay, Western Australia, is a natural laboratory to study in situ stromatolitic carbonate formation in a hypersaline lagoon. Stromatolitic carbonates sampled at three different tidal environments (supratidal, intertidal and subtidal; cf. Martin et al., 2023) show a gradual increase in Ba isotopic compositions (d¹³⁸Ba) from -0.12 ‰ to modern open ocean values (up to 0.6 ‰) with decreasing Ba concentrations following classic Rayleigh pattern. Declining Ba/Ca ratios (0.93 to 0.32) follow conservative mixing trends with increasing Co, Li, Sr and Ni concentrations from the shore to subtidal environments. Due to the lack of riverine influx into Shark Bay, groundwater discharge is the likeliest source for two end-members mixing with seawater. We observe fingerprints of the groundwater end-member in a supratidal sample showing particular low, stable Ba isotope values (-0.12 ‰), which further corresponds with elevated Mn/Sr ratios and the lowest O isotope compositions (2.9 ‰) as an indicator for a meteoric origin. This end-member likely reflects carbonate precipitation near shore under the influence of groundwater discharge and reaction with high alkalinity fluids derived from the local Tamala Limestone aquifer (d¹³⁸Ba = 0.09 to 0.24 ‰ at 0.3 to 19 PSU; cf., Mayfield et al., 2021). In contrast, the stromatolitic carbonates that form in equilibrium with a saline end-member show heavy Ba isotope compositions (0.57‰).

Injection of alkaline groundwaters into the hypersaline waters of Hamelin Pool likely contributed to an enhanced rate of carbonate precipitation, possibly catalysed by nucleation within or onto extra-polymeric substances of diverse microbial mats. Interaction of benthic microbes, especially cyanobacteria, in alkaline waters may offer promising carbon sequestration pathways in the modern high pCO₂ atmosphere and small-scale mitigation to the harmful impacts of the current climate crisis.

References: Martin et al., 2023, GCA; Mayfield et al., 2021, Nature Communications